1,4-Dioxacylcloalkane-2-one and 1,4-dioxacycloalkene-2-one

ABSTRACT

The present invention relates to novel macrocyclic compounds, and to their preparation and use in perfumes. Specifically, the present invention relates to novel 1,4-dioxacycloalkan-2ones and 1,4-dioxzcycloaken-2-ones.

FIELD OF THE INVENTION

The invention relates to novel 1,4-dioxacycloalkan-2-ones and1,4-dioxacycloalken-2-ones, and to their preparation and use infunctional perfumery and in fine perfumery.

BACKGROUND OF THE INVENTION

Compounds with a musk odor are sought-after components in the fragranceindustry. They are characterized both by their property of impartingradiance to perfume compositions and also by their ability to act asfixative. For this reason, musk fragrances are nowadays used in manyperfume compositions.

Typical musk fragrances are characterized by a macrocyclic ring having13 to 17 carbon atoms which carries a ketone or an ester as functionalgroup. Moreover, macrocyclic musk fragrances which carry two functionalgroup are also known, e.g. 1,7-dioxacycloalkan-8-ones (EP A 884,315).However, the functional groups of these molecules are distributed overboth hemispheres of macrocycles. Preference is, however, given tomacrocyclic compounds in which the functional groups are concentrated inone part of the molecule since, in so doing, a stronger bond to theactive center of the receptor and, consequently, a lower threshold valuecan be expected.

Because the costs of starting materials for the preparation aresometimes high and because of the extremely high synthesis complexity,the number of macrocyclic compounds available to the perfumer for thecomposition of perfumes is relatively limited (K. Bauer, D. Garbe, H.Surburg, Common Fragrance and Flavor Materials, Wiley-VCH, 3^(rd)Edition, 1997, 67 to 68 and 117 to 122). There is an urgent need forfurther macrocyclic compounds which can be prepared in an efficientsynthesis from favorable starting materials and, moreover, extend theperfumer's options with their original scent properties.

The class of nature-similar macrocyclic musk fragrances will become moreand more important in the future since the synthetic musk compounds ofthe nitroaromatic and polycyclic series are persistent and lipophilic,meaning that these compounds accumulate in aquatic food chains and fattytissue (H. Brunn, G. Rimkus, Ernährungs-Umschau 1996, 43, 442 to 449; H.Brunn, G. Rimkus, Ernährungs-Umschau 1997, 44, 4 to 9).

SUMMARY OF THE INVENTION

It was therefore the object to extend the raw material palette availablefor composing perfume through novel macrocyclic musk compounds withoriginal odiferous properties.

Furthermore, it should be possible to prepare the novel musk fragrancesin a cost-effective manner.

DETAILED DESCRIPTION OF THE INVENTION

We have now found novel 1,4-dioxacycloalkan-2-ones and1,4-dioxacycloalken-2-ones of the formula

in which

the dashed bond is a single or E/Z double bond,

where in the case of a double bond being present in the ring, thecompounds can be in the E and Z form, and

compounds with a chiral center can be either in the (R) or (S) form, orelse can be present as an enantiomer mixture,

R¹ and R² are identical or different and are hydrogen or lower alkyl,

x is a saturated alkylene chain having 1 to 4 carbon atoms and

y is a saturated alkylene chain having 4 to 10 carbon atoms,

where saturated compounds

in which R¹ and R² are hydrogen and x+y=11 carbon atoms and

in which R¹ is methyl and R² is hydrogen and x+y=8 carbon atoms, areexcluded.

Lower alkyl generally means a saturated hydrocarbon radical having 1 to6 carbon atoms. Examples which may be mentioned are: methyl, ethyl,propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl andisohexyl.

Preferred radicals are hydrogen, methyl and ethyl.

An alkylene chain having 1 to 4 carbon atoms generally means methylene,ethylene, propylene and butylene.

Preference is given here to: methylene, ethylene and butylene.

An alkylene chain having 4 to 10 carbon atoms generally means butylene,pentylene, hexylene, heptylene, octylene, nonylene and decylene.

Preference is given here to: butylene, octylene and nonylene.

The novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-onesaccording to the invention accordingly include 14- to 18-memberedsaturated or unsaturated, unsubstituted or lower-alkyl-substituted1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones.

Specifically, mention may be made of the following1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones:

1,4-dioxa-(E/Z)-9-cyclotetradecen-2-one

1,4-dioxacyclotetradecan-2-one

3-methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one

3-methyl-1,4-dioxacyclopentadecan-2-one

1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one

1,4-dioxacyclopentadecan-2-one

3-methyl-1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one

3-methyl-1,4-dioxacyclohexadecan-2-one

1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one

1,4-dioxacyclohexadecan-2-one

1,4-dioxa-(E/Z)-7-cyclohexadecen-2-one

1,4-dioxa (E/Z)-7-cycloheptadecen-2-one

3-methyl-1,4-dioxa-(E/Z)-7-cyclohexadecen-2-one

3-methyl-1,4-dioxa-(E/Z)-7-cycloheptadecen-2-one

3-methyl-1,4-dioxacycloheptadecan-2-one

The 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones accordingto the invention in which the functional groups are in close proximityto one another achieve said object in an ideal manner. As well asperfumistically interesting musk-like odor notes, they are characterizedby very good adhesion, coupled with a low threshold value.

The saturated 1,4-dioxacycloalkan-2-ones, methyl-substituted in the 3position, in particular 3-methyl-1,4-dioxacyclopentadecan-2-one and3-methyl-1,4-dioxacyclohexadecan-2-one, have particularly attractiveolfactory odor properties. They are characterized by a sweet,woody-ambergris, animalic, erogenous and thus very natural musk note.The olfactory profile of the unsaturated3-methyl-1,4-dioxacyloalken-2-ones is very similar to that of thesaturated compounds, although the intensity is lower. For comparison,the analogous 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-oneswithout methyl substitution in the 3 position have been synthesized.Surprisingly, in the case of the unsaturated 1,4-dioxacycloalken-2-ones,the erogenous and animalic aspects are pushed into the background infavor of metallic, pressing iron-like odor descriptions. The saturated1,4-dioxacycloalkan-2-ones, by contrast, and here in particular1,4-dioxacyclohexadecan-2-one are characterized again by a very nicenatural musk-like character.

In contrast to the known 1,4-dioxacycloheptadecan-2-one and3-methyl-1,4-dioxacyclotetradecan-2-one, the 1,4-dioxacycloalkan-2-onesand 1,4-dioxacycloalken-2-ones according to the invention surprisinglyhave a very much more natural musk note, coupled with nitromusk andambrette musk aspects.

We have found a process for the preparation of novel1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones of the formula

in which

the dashed bond is a single or E/Z double bond,

where in the case of a double bond being present in the ring, thecompounds can be in the E and Z form, and

compounds with a chiral center can be either in the (R) or (S) form, orelse can be present as an enantiomer mixture,

R¹ and R² are identical or different and are hydrogen or lower alkyl,

x is a saturated alkylene chain having 1 to 4 carbon atoms and

y is a saturated alkylene chain having 4 to 10 carbon atoms,

where saturated compounds

in which R¹ and R² are hydrogen and x+y=11 carbon atoms and

in which R¹ is methyl and R² is hydrogen and x+y=8 carbon atoms, areexcluded, found,

which is characterized in that alkylcarboxylic acids or esters thereofwhich can be derivatized in the 2 position and are of the formula

in which

R¹ has the meaning given above, and

R³ is OH, Cl, Br and

R⁴ is OH, OMe or OEt,

are used, which, in the 1st step, are etherified, in a 2nd step areesterified and in a 3rd step the ring is closed by olefine metathesis togive the unsaturated 1,4-dioxacycloalken-2-ones, which are thenoptionally hydrogenated in a 4th step to give the saturated1,4-dioxacycloalkan-2-ones.

In the 1st step, where R³=OH and R⁴=OMe or OEt, deprotonation is carriedout with one equivalent of sodium hydride as base in tetrahydrofuran assolvent. 1.5 equivalents of the [lacuna],ω-alkene halide are then added,after which the reaction mixture is refluxed, giving the2-alkenyloxycarboxylic esters (Tetrahedron Lett. 1976, 17, 3535).

In the case of the α-halocarboxylic acids (R³=Cl, Br and R⁴=OH) asstarting compounds, 2 to 3 equivalents of sodium hydride are required,the α,ω-alkenol firstly being deprotonated before the α-halocarboxylicacid is added. This mixture too is refluxed in order to obtain the2-alkenyloxycarboxylic acids (J. Org. Chem. 1998, 63, 3160).

The 2-alkenyloxycarboxylic acids (R⁴=OH) synthesized in the mannerdescribed above are esterified in the 2nd step with the addition of from1 to 3 equivalents of the corresponding α,ω-alkenol and 0.1 to 5 mol %of p-toluenesulfonic acid with a water separator using toluene asentrainer to give the doubly terminally unsaturated2-alkenyloxycarboxylic alkenyl esters.

If the 2-alkenyloxycarboxylic esters (R⁴=OMe, OEt) are present, theseare firstly hydrolyzed with 1.5 to 2 equivalents of LiOH inmethanol/water (ratio:3:1) in order then to be esterified with 1 to 3equivalents of the corresponding α,ω-alkenol and 0.1 to 5 mol % of0p-toluenesulfonic acid with a water separator to give the doublyterminally unsaturated 2-alkenyloxycarboxylic alkenyl esters.

The intermediates which form here are the novel doubly terminallyunsaturated 2-alkenyloxycarboxylic alkenyl esters of the formula

in which R¹, R², x and y have the meaning given above.

The 1,4-dioxacycloalken-2-ones according to the invention are prepared(3rd step) starting from the doubly terminally unsaturated2-alkenyloxycarboxylic alkenyl esters in a ring closure olefinmetathesis (U.S. Pat. No. 4,490,404; D. Tetrahedron lett., 1980, 21,1715; JP 10 175,882). For this, the 2-alkenyloxycarboxylic alkenyl esteris refluxed for one hour in a 0.01 to 0.003 molar dichloromethanesolution with 0.1 to 0.5 equivalents of titanium tetraisopropoxide. Thesubsequent addition of from 0.5 to 5 mol % ofbenzylidene-bis-tricyclohexylphosphine)-dichlororuthenium (Grubbscatalyst) and reheating at reflux temperature for 8 to 48 hours(Synthesis, 1997, 792; Synlett, 1997, 1010) produces the1,4-dioxacycloalken-2-ones according to the invention.

The hydrogenation (4th step) at standard hydrogen pressure and roomtemperature with 1 to 5% by weight of Pd/C in isopropanol produces the1,4-dioxacycloalkan-2-ones according to the invention starting from the1,4-dioxacycloalken-2-ones according to the invention.

The process according to the invention can be illustrated using theexample of 3-methyl-1,4-dioxacyclopentadecan-2-one by the followingequation:

We have found a further process for the preparation of the novel chiral3-alkyl-1,4-dioxacycloalkan-2-ones and3-alkyl-1,4-dioxacycloalken-2-ones of the formula

in which the dashed bond is a single or E/Z double bond,

where in the case of a double bond being present in the ring, thecompounds can be in the E and Z form,

and the compounds with a chiral center are present in the (R) or (S)form,

R¹ is lower alkyl and

x is a saturated alkylene chain having 1 to 4 carbon atoms and

y is a saturated alkylene chain having 4 to 10 carbon atoms,

which is characterized in that the starting materials used are (S)-2- or(R)-2-hydroxycarboxylic alkyl esters of the formula

in which

R¹ has the meaning given above, and

R⁵ is a C₁ to C₈ alkyl radical,

which are etherified in a 1st step under acidic, nonracemizingconditions, are transesterified in a 2nd step under Lewis acid catalysisand in a 3rd step the ring is closed by olefin metathesis to give theunsaturated 3-alkyl-1,4-dioxacycloalken-2-ones, which are thenoptionally hydrogenated in a 4th step to give the saturated3-alkyl1,4-dioxacycloalkan-2-ones.

In the 1st step, the O-alkylation of the (R)- or (S)-2-hydroxycarboxylicalkyl esters is carried out via the trichloroacetimidate methods(Tetrahedron Lett., 1988, 29, 4139-4142). For this, 2 to 3 equivalentsof the alkenyl trichloroacetimidate and 5 to 15 mol % oftrifluoromethanesulfonic acid are added to the chiral2-hydroxycarboxylic alkyl esters in cyclohexane. After 16 to 24 hours atroom temperature, the chiral (R)- or (S)-2-alkenyloxycarboxylic alkylesters are obtained. The enantiomeric excesses of these compounds are≧95%.

In the subsequent transesterification (2nd step), the chiral2-alkenyloxycarboxylic ester is reacted with 1 to 3 equivalents of thecorresponding [lacuna],ω-alkenol, with the addition of from 1 to 10 mol% of titanium tetraisopropoxide (Tetrahedron Lett., 1998, 4223-4226).This gives the chiral, doubly terminally unsaturated2-alkenyloxycarboxylic alkenyl esters.

The chiral doubly terminally unsaturated 2-alkenyloxycarboxylic alkenylesters of the formula

in which R^(1′), x and y have the meaning given above are novel.

The enantiomeric excesses of these compounds are ≧95%.

The preparation of the novel chiral 3-alkyl-1,4-dioxacycloalken-2-onesand 3-alkyl-1,4-dioxacycloalkan-2-ones is carried out in accordance withthe methods described above, via ring closure olefin metathesis (3rdstep) and subsequent hydrogenation (4th step).

The enantiomeric excesses of the saturated3-alkyl-1,4-dioxacycloalkan-2-ones are ≧95%.

The process according to the invention can be illustrated using theexample of (S)-(−)-3-methyl-1,4-dioxacyclopentadecan-2-one by thefollowing equation:

Specifically, the following chiral 3-alkyl-1,4-dioxacycloalkan-2-onesand 3-alkyl-1,4-dioxacycloalken-2-ones may be mentioned:

(S)-(−)-3-methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one

(S)-(−)-3-methyl-1,4-dioxacyclopentadecan-2-one

(S)-(−)-3-methyl-1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one

(S)-(−)-3-methyl-1,4-dioxacyclohexadecan- 2-one

(R)-(+)-3-methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one

(R)-(+)-3-methyl-1,4-dioxacyclopentadecan-2-one

(R)-(+)-3-methyl-1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one

(R)-(+)-3-methyl-1,4-dioxacyclohexadecan-2-one

The novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones canbe used here as individual substances in a large number of products;they can be particularly advantageously combined with other fragrancesto give new types of perfume compositions.

By using the novel 1,4-dioxacycloalkan-2-ones and1,4-dioxacycloalken-2-ones, it is generally possible, even in a lowconcentration, to achieve fine, erogenous musk notes in the resultingperfume compositions, the overall odor impression being remarkablyharmonized, the radiance be detectably increased and the fixing, i.e.the adhesive power of the perfume oil, being considerably intensified.

Examples of fragrances with which the novel 1,4-dioxacycloalkan-2-onesand 1,4-dioxacycloalken-2-ones can be advantageously combined are given,for example, in S. Arctander, Perfume and Flavor Materials, Vol. I andII, Montclair, N. J., 1969, Selbstverlag oder K. Bauer, D. Garbe and H.Surburg, Common Fragrance and Flavor Materials, 3^(rd). Ed., Wiley-VCH,Weinheim 1997.

Specifically, mention may be made of:

extracts from natural raw materials such as essential oils, concretes,absolutes, resins, resinoids, balsams, tinctures, such as, for example,ambergris tincture; amyris oil; angelica seed oil; angelica root oil;aniseed oil; valerian oil; basil oil; wood moss absolute; bay oil;mugwort oil; benzoin resin; bergamot oil; beeswax absolute; birch taroil; bitter almond oil; savory oil; bucco leaf oil; cabreuva oil; cadeoil; calmus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil;cassia oil; cassia absolute; castoreum absolute; cedar leaf oil;cedarwood oil; cistus oil; citronella oil; lemon oil; copaiva balsam;copaiva balsam oil; coriander oil; costus root oil; cumin oil; cypressoil; davana oil; dill herb oil; dill seed oil; eau de brouts absolute;oakmoss absolute; elemi oil; estragon oil; eucalyptus citriodora oil;eucalyptus oil; fennel oil; spruce needle oil; galbanum oil; galbanumresin; geranium oil; grapefruit oil; guaiac wood oil; gurjun balsam;gurjun balsam oil; helichrysum absolute; helichrysum oil; ginger oil;iris root absolute; iris root oil; jasmine absolute; calamus oil; bluecamomile oil; Roman camomile oil; carrot seed oil; cascarilla oil; pineneedle oil; spearmint oil; caraway oil; labdanum oil; labdanum absolute;labdanum resin; lavandin absolute; lavandin oil; lavender absolute;lavender oil; lemongrass oil; lovage oil; distilled lime oil; pressedlime oil; linaloe oil; litsea cubeba oil; bayleaf oil; mace oil;marjoram oil; mandarin oil; massoi bark oil; mimosa absolute; musk seedoil; musk tincture; clary sage oil; nutmeg oil; myrrh absolute; myrrhoil; myrtle oil; clove leaf oil; clove flower oil; neroli oil; olibanumabsolute; olibanum oil; opopanax oil; orange-flower absolute; orangeoil; origanum oil; palmarosa oil; patchouli oil; perilla oil; Peruvianbalsam oil; parsley leaf oil; parsley seed oil; petitgrain oil;peppermint oil; pepper oil; pimento oil; pine oil; pennyroyal oil; roseabsolute; rosewood oil; rose oil; rosemary oil; Dalmation sage oil;Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil;Japanese anise oil; styrax oil; tagetes oil; fir needle oil; tea-treeoil; turpentine oil; thyme oil; Tolu balsam; tonka absolute; tuberoseabsolute; vanilla extract; violet leaf absolute; verbena oil; vetiveroil; juniper oil; wine lees oil; absinthe oil; wintergreen oil; ylangoil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil;and fractions thereof, or ingredients isolated therefrom;

individual fragrances from the group of hydrocarbons, such as, forexample, 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene;p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene;limonene; longifolene; myrcene; ocimene; valencene;(E,Z)-1,3,5-undecatriene;

of aliphatic alcohols, such as, for example, hexanol; octanol;3-octanol; 2,6-dimethylheptanol; 2-methylheptanol, 2-methyloctanol;(E)-2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol; mixture of3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol;3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol;4-methyl-3-decen-5-ol; of aliphatic aldehydes and1,4-dioxacycloalken-2-ones thereof, such as, for example, hexanal;heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal;2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal;2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal;2,6,10-trimethyl-5,9-undecadienal; heptanal diethyl acetal;1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyl oxyacetaldehyde;

of aliphatic ketones and oximes thereof, such as, for example,2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone;5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; ofaliphatic sulfur-containing compounds, such as, for example,3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercapto-hexanol;3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexylacetate; 1-menthene-8-thiol; of aliphatic nitriles, such as, forexample, 2-nonenenitrile; 2-tridecenenitrile; 2,12-tridecienenitrile;3,7-dimethyl-2,6-octadienenittile; 3,7-dimethyl-6-octenenitrile;

of aliphatic carboxylic acids and esters thereof, such as, for example,(E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate;hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate;(E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate;3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate;isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl isobutyrate;hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethylhexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyloctanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octynate; methyl2-nonynate; allyl 2-isoamyloxy-acetate ; methyl3,7-dimethyl-2,6-octadienoate;

of acyclic terpene alcohols, such as, for example, citronellol;geraniol; nerol; linalool; lavadulol; nerolidol; farnesol;tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol;2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol;2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5- octadien-2-ol;3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl- 1,5,7-octatrien-3-ol2,6-dimethyl-2,5,7-octatrien-1-ol; and formates, acetates, propionates,isobutyrates, butyrates, isovalerates, pentanoates, hexanoates,crotonates, tiglinates, 3-methyl-2-butenoates thereof;

of acyclic terpene aldehydes and ketones, such as, for example,geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal;7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethyl acetals of geranial, neral,7-hydroxy-3,7-dimethyloctanal;

of cyclic terpene alcohols, such as, for example, menthol; isopulegol;alpha-terpineol; terpineol-4; menthan-8-ol; menthan-1-ol; menthan-7-ol;borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol;guaiol; and formates, acetates, propionates, isobutyrates, butyrates,isovalerates, pentanoates, hexanoates, crotonates, tiglinates,3-methyl-2-butenoates thereof;

of cyclic terpene aldehydes and ketones, such as, for example, menthone;isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone;alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone;alpha-isomethylionone; beta-isomethylionone; alpha-irone;alpha-damascone; beta-damascone; beta-damascenone; delta-damascone;gamma-damascone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one; nootkatone; dihydronootkatone;alpha-sinensal; beta-sinensal; acetylated cedarwood oil (methyl cedrylketone);

of cyclic alcohols, such as, for example, 4-tert-butylcyclohexanol;3,3,5-trimethyl-cyclohexanol; 3-isocamphylcyclohexanol;2,6,9-trimethyl-Z2,Z5,E9-cyclo dodecatrien-1-ol;2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

of cycloaliphatic alcohols, such as, for example,alpha,3,3-trimethylcyclohexyl -methanol;2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol;2-methyl-4-(2,2,3-trimethyl-3-cyclopent- 1-yl)-2-buten-1-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopent- 1-yl)-2-buten-1-ol;3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-pentan-2-ol;3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol;3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol;1-(2,2,6-trimethylcyclohexyl)pentan-3-ol;1-(2,2,6-trimethylcyclohexyl)hexan-3-ol;

of cyclic and cycloaliphatic ethers, such as, for example, cineol;cedryl methyl ether; cyclododecyl methyl ether;(ethoxymethoxy)cyclododecane; alpha-cedrene epoxide;3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan;3a-ethyl-6,6,9a-trimethyl -dodecahydronaphtho[2,1-b]furan;1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide;2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;

of cyclic ketones, such as, for example, 4-tert-butylcyclohexanone;2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone;2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one;3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one;3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone;3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone;4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone;4-tert-pentylcyclohexanone; 5-cyclohexadecen-1-one;6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone;5-cyclohexadecen-1-one; 8-cyclohexadecen-1-one; 9-cycloheptadecen-1-one;cyclopentadecanone;

of cycloaliphatic aldehydes, such as, for example,2,4-dimethyl-3-cyclohexene-carbaldehyde;2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal;4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde;4-(4-methyl-3-penten-1-yl)-3-cyclo-hexenecarbaldehyde;

of cycloaliphatic ketones, such as, for example,1-(3,3-dimethylcyclohexyl)-4-penten-1-one;1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one;2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methylketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone;tert-butyl 2,4-dimethyl-3-cyclohexen-1-yl ketone;

of esters of cyclic alcohols, such as, for example,2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate;2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate;decahydro-2-naphthyl acetate; 3-pentyltetrahydro-2H-pyran-4-yl acetate;decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate;4,7-methano-3a,4,5,6,7,7a-hexa-hydro-5 or 6-indenyl acetate;4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate;4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate;4,7-methanooctahydro-5 or 6-indenyl acetate;

of esters of cycloaliphatic carboxylic acids, such as, for example,allyl 3-cyclohexyl-propionate; allyl cyclohexyloxyacetate; methyldihydrojasmonate; methyl jasmonate; methyl2-hexyl-3-oxocyclopentanecarboxylate; ethyl2-ethyl-6,6-dimethyl-2-cyclo-hexenecarboxylate; ethyl2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl2-methyl-1,3-dioxolan-2-acetate;

of aromatic hydrocarbons, such as, for example, styrene anddiphenylmethane;

of araliphatic alcohols, such as, for example, benzyl alcohol;1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenylpropanol;2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol;2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethylalcohol; 1,1-dimethyl-3-phenylpropanol;1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol;3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzylalcohol; 1-(4-isopropylphenyl)ethanol;

of esters of araliphatic alcohols and aliphatic carboxylic acids, suchas, for example, benzyl acetate; benzyl propionate; benzyl isobutyrate;benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate;2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethylacetate; alpha-trichloromethylbenzyl acetate;alpha,alpha-dimethylphenylethyl acetate; alpha,alpha-dimethylphenylethylbutyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzylacetate; of araliphatic ethers, such as, for example, 2-phenylethylmethyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl 1-ethoxyethylether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethylacetal; hydratropaaldehyde dimethyl acetal; phenylacetaldehyde glycerolacetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxanes;4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxin;4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxin;

of aromatic and araliphatic aldehydes, such as, for example,benzaldehyde; phenyl-acetaldehyde; 3-phenylpropanal; hydratropaaldehyde;4-methylbenzaldehyde; 4-methylphenylacetaldehyde;3-(4-ethylphenyl)-2,2-dimethylpropanal;2-methyl-3-(4-isopropylphenyl)propanal;2-methyl-3-(4-tert-butylphenyl)propanal; 3-(4-tert-butylphenyl)propanal;cinnamaldehyde; alpha-butylcinnamaldehyde; alpha-amyl-cinnamaldehyde;alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal;4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde;4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde;3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal;2-methyl-3-(4-methylenedioxyphenyl) -propanal;

of aromatic and araliphatic ketones, such as, for example, acetophenone;4-methylacetophenone; 4-methoxyacetophenone;4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone;4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl) -ethanone;benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone;6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone;1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone;5′,6′,7′,8′-tetrahydro-3′,5′,5′,6′,8′,8′-hexamethyl-2-acetonaphthone;

of aromatic and araliphatic carboxylic acids and esters thereof, suchas, for example, benzoic acid; phenylacetic acid; methyl benzoate; ethylbenzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethylphenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methylcinnmate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate;cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamylsalicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenylsalicylate; benzyl salicylate; phenylethyl salicylate; methyl2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidate; ethyl3-methyl-3-phenylglycidate;

of nitrogen-containing aromatic compounds, such as, for example,2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene;3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile;5-phenyl-3-methyl-2-pentenenitrile; 5-phenyl-3-methylpentanenitrile;methyl anthranilate; methy N-methylanthranilate; Schiff bases of methylanthranilate with 7-hydroxy-3,7-dimethyloctanal,2-methyl-3-(4-tert-butylphenyl)propanal or2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-isopropylquinoline;6-isobutylquinoline; 6-sec-butylquinoline; indole; skatole;2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

of phenols, phenyl ethers and phenyl esters, such as, for example,estragole; anethole; eugenole; eugenyl methyl ether; isoeugenole;isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether;beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-naphthylisobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate;2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresylphenylacetate;

of heterocyclic compounds, such as, for example,2,5-dimethyl-4-hydroxy-2H-furan-3-one;2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one;3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;

of lactones, such as, for example, 1,4-octanolide;3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide;8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide;1,5-dodecanolide; 1,15-pentadecanolide; cis- andtrans-11-pentadecen-1,15-olide; cis- and trans-12-pentadecen-1,15-olide;1,16-hexadecanolide; 9-hexadecen-1,16-oide; 10-oxa-1,16-hexadecanolide;11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene1,12-dodecanedioate; ethylene 1,13-tridecanedioate; coumarin;2,3-dihydrocoumarin; octahydrocoumarin.

The perfume oils comprising the 1,4-dioxacycloalkan-2-ones and1,4-dioxacycloalken-2-ones according to the invention can be used inliquid form, neat or diluted with a solvent for perfumings. Suitablesolvents for this purpose are, for example, ethanol, isopropanol,diethylene glycol monoethyl ether, glycerol, propylene glycol,1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethylcitrate, isopropyl myristate etc.

In addition, the perfume oils comprising the 1,4-dioxacycloalkan-2-onesand 1,4-dioxacycloalken-2-ones according to the invention can beadsorbed on a carrier which serves both to distribute the fragrancesfinely within the product and to release them in a controlled mannerduring use. Such carriers can be porous inorganic materials such aslight sulfate, silica gels, zeolites, gypsums, clays, clay granules, gasconcrete etc. or organic materials such as woods and cellulose-basedsubstances.

The perfume oils comprising the 1,4-dioxacycloalkan-2-ones and1,4-dioxacycloalken-2-ones according to the invention can also bemicroencapsulated, spray dried, in the form of inclusion complexes or inthe form of extrusion products and be added in this form to the productto be perfumed.

The properties of the perfume oils modified in this way can optionallybe further optimized by “coating” with suitable materials with regard toa more targeted scent release, for which purpose preference is given tousing wax-like polymers, such as, for example, polyvinyl alcohol.

The microencapsulation of the perfume oils can, for example, be carriedout by the “coacervation method” using capsule materials made from, forexample, polyurethane-like substances or soft gelatin. The spray-driedperfume oils can, for example, be prepared by spray drying an emulsionor dispersion comprising the perfume oil, where the carriers used can bemodified starches, proteins, dextrin and vegetable gums. Inclusioncomplexes can be prepared, for example, by introducing dispersions ofthe perfume oil and cyclodextrins or urea derivatives into a suitablesolvent, e.g. water. Extrusion products can arise by melting the perfumeoils with a suitable wax-like substance and by extrusion with subsequentsolidification, optionally in a suitable solvent, e.g. isopropanol.

In perfume compositions, the amount of 1,4-dioxacycloalkan-2-ones and1,4-dioxacycloalken-2-ones according to the invention used is 0.05 to50% by weight, preferably 0.5 to 20% by weight, based on the totalperfume oil.

The perfume oils comprising the 1,4-dioxacycloalkan-2-ones and1,4-dioxacycloalken-2-ones according to the invention can be used inconcentrated form, in solutions or in the above-described modified formfor the preparation of, for example, perfume extracts, eaux de parfum,eaux de toilette, aftershaves, eaux de cologne, pre-shave products,splash colognes and perfumed freshening wipes, and the perfuming ofacidic, alkaline and neutral cleaners, such as, for example, floorcleaners, window cleaners, dishwashing detergents, bath and sanitarycleaners, scouring milk, solid and liquid WC cleaners, pulverulent andfoam carpet cleaners, liquid laundry detergents, pulverulent laundrydetergents, laundry pretreatment agents, such as bleaches, soakingagents and stain removers, fabric softeners, washing soaps, washingtablets, disinfectants, surface disinfectants, and of air fresheners inliquid or gel form or deposited on a solid carrier, aerosol sprays,waxes and polishes, such as furniture polishes, floor waxes, shoecreams, and bodycare compositions, such as, for example, solid andliquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bathoils, cosmetic emulsions of the oil-in-water, water-in-oil andwater-in-oil-in-water type, such as, for example, skin creams andlotions, face creams and lotions, sunscreen creams and lotions, aftersuncreams and lotions, hand creams and lotions, foot creams and lotions,depilatory creams and lotions, aftershave creams and lotions, tanningcreams and lotions, haircare products, such as, for example, hairsprays,hair gels, hairsetting lotions, hair rinses, permanent and semipermanenthair colorants, hair-shaping compositions, such as cold waves andhair-smoothing compositions, hair tonics, hair creams and lotions,deodorants and antiperspirants, such as, for example, underarm sprays,roll-ons, deodorant sticks, deodorant creams, products in decorativecosmetics, such as, for example, eyeshadows, nail varnishes,foundations, lipsticks, mascara, and of candles, lamp oils, joss-sticks,insecticides, repellents, propellants.

One important use of the 1,4-dioxacycloalkan-2-ones and1,4-dioxacycloalken-2-ones according to the invention is in theperfuming of soaps and laundry detergents because of their stability inthe alkaline range. In the case of the use in laundry detergentperfumings, the 1,4-dioxacycloalkan-2-ones and1,4-dioxacycloalken-2-ones according to the invention are distinguishedby a substantivity which is greater than that of fragrances usedhitherto, i.e. by increased absorptive power and increased adhesion ofthe fragrance to the washed fibers.

The compounds below illustrate the invention:

EXAMPLES Example 1 1,4-Dioxacyclotetradecan-2-one

Hex-5-enyl 2-bromoacetate: 6.2 g (30 mmol) of DCC are added to asolution, cooled to 0° C., of 4.1 g (30 mmol) of bromoacetic acid, 250mg (3 mmol) of DMAP and 3.3 g (33 mmol) of 5-hexen-1-ol in 30 ml ofCH₂Cl₂. When the addition is complete, the mixture is left to reach roomtemperature and stirred overnight. If the reaction is complete, theprecipitated urea derivative is filtered off, the filtrate isconcentrated by evaporation and the residue is taken up in n-pentane.The mixture is then filtered again and the filtrate is then washed twicewith 0.5N HCl and once with saturated NaHCO₃ solution. The resultingcrude product is used in the next reaction without further purification.

Hex-5-enyl 2-(5-hexenyloxy)-acetate (x, y=4, R¹, R²=H): 3,5 g (34 mmol)of 5-hexen-1-ol, dissolved in 25 ml of THF, are added dropwise to asuspension of 0.95 g (28 mmol) of NaH in 20 ml of THF. When the additionis complete, 4.8 g (23 mmol) of hex-5-enyl 2-bromoacetate, dissolved in15 ml of THF, are added dropwise. The mixture is then refluxedovernight. When the reaction is complete, the mixture is left to cooland quenched with 2N HCl. After the phases have separated, the aqueousphase is extracted again with Et₂O and twice with EtOAc. The combinedorganic phases are dried over Na₂SO₄, filtered and evaporated on arotary evaporator. The crude product is purified on silica gel(cyclohexane/EtOAc=40:1; R_(f)=0.26), giving, as product, a colorlessoil in a yield of 4.8 g (67% over 2 stages).

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.38-1.56 (m, 4H), 1.56-1.76 (m, 4H),2.0-2.16 (m, 4H), 3.51 (t, J=6.4 Hz, 2H), 4.07 (s, 2H), 4.17 (t, J=6.4Hz, 2H), 4.99-5.08 (m, 4H), 5.73 (ddd, J=17.2, 10.2, 5.8 Hz, 1H), 5.86(ddd, J=17.2, 10.2, 5.8 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=25.0, 25.2, 27.9, 28.9, 33.2, 33.4,64.6, 68.2, 71.6, 114.5, 114.8, 138.1, 138.4, 170.5

The ring closure olefin metathesis and subsequent hydrogenation werecarried out analogously to the procedures described under Example 2.1.Only the spectroscopic data are thus given here:

1,4-dioxa-(E/Z)-9-cyclotetradecen-2-one (x, y=4, R¹, R²=H)

Odor: woody, cedary, patchouli, musk.

Isomerism details: excess:deficit isomer

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.33-1.83 (m, 8H), 1.95-2.16 (m, 4H),3.53 (t, J=6.5 Hz, 2H), 4.07:4.05 (s, 2H), 4.17-4.33 (m, 2H), 5.25-5.70(m, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=25.2, 25.4, 25.6, 26.4, 26.7, 27.9,63.8:64.6, 69.6: 68.9, 70.7, 71.7, 129.6:130.7, 130.0:131.3, 171.2.

1,4-dioxacyclotetradecan-2-one (x, y=4, R¹, R²=H)

Odor: woody, patchouli, musk, erogenous, metallic, reminiscent of a hotiron.

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.27-1.56 (m, 12H), 1.60-1.77 (m, 2H),3.53 (t, J=6.4 Hz, 2H), 4.09 (s, 2H), 4.26 (dd, J=5.42, 4.42 Hz, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=23.9, 24.0, 24.6, 25.3, 25.5, 25.6,26.9, 27.5, 64.8, 69.4, 70.4, 170.9.

Example 2.1 (RS)-3-Methyl-1,4-dioxacyclopentadecan-2-one

Ethyl (RS)-2-allyloxy-propionate (x=1, Y=OEt, R¹=Me, R²=H): 23.6 g (0.2mol) of ethyl (S)-(−)-lactate, dissolved in 100 ml of THF, are added toa suspension of 8.0 g (0.2 mol) of NaH in 150 ml THF. When the additionis complete, 36.3 g (0.3 mol) of allyl bromide, dissolved in 10 ml ofTHF, are added dropwise. Some KI is then added and the mixture isrefluxed for 16 h. The mixture is then cooled and the reaction isquenched with 100 ml of 2N HCl. The aqueous phase is extracted twicemore with Et₂O before the combined organic phases are dried over Na₂SO₄.The mixture is then filtered and the filtrate is evaporated to drynesson a rotary evaporator, giving 31.7 g of crude product (GC purity89.0%), which is used in the next reactions without furtherpurification.

Dec-9-enyl (RS)-2-allyloxy-propionate (x=1, y=8, R¹=Me, R²=H): 3,5 g ofcrude ethyl (RS)-2-allyloxy-propionate are introduced into 24 ml ofMeOH/H₂O=3:1, cooled to 0° C., and then 2.2 g (30 mmol) of LiOH·H₂O areadded in portions. The mixture is further stirred for 5 minutes beforethe ice cooling is removed and the mixture is stirred for a further 1 hat room temperature. Methanol is then removed on a rotary evaporator andthe residue is taken up in water. The aqueous phase is firstly extractedwith Et₂O in order then to be acidified to pH 1 with 6N HCl. The aqueousphase is then saturated with NaCl and extracted three times with EtOAc.The combined organic phases are dried over Na₂SO₄, filtered and freedfrom solvent on a rotary evaporator. The resulting carboxylic acid isdissolved in 40 ml of toluene and treated with 4.7 g (30 mmol) of9-decen-1-ol and 0.38 g (2 mmol) of p-toluenesulfonic acid. The mixtureis then heated using a water separator until visible amounts of water nolonger separate out. After cooling to room temperature, the reactionsolution is once again wash ed with saturated NaHCO₃ solution, thendried over Na₂SO₄, filtered and freed from solvent on a rotaryevaporator. Flash chromatography (cyclohexane/EtOAc=20:1, R_(f)=0.31)over silica gel gives 2.8 g (52.2%) of dec-9-enyl(RS)-2-allyloxy-propionate as a colorless oil.

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.25-1.40 (m, 10H), 1.42 (d, J=6.9 Hz,3H), 1.57-1.74 (m, 2H), 1.97-2.13 (m, 2H), 3.94 (ddd, J=12.5, 5.9, 1.7Hz, 2H), 4.02 (q, J=6.7 Hz, 1H), 4.14 (m, 2H), 4.93 (ddd, 1H, J=10.2,2.2, 1.1 Hz, 1H), 4.99 (ddd, J=17.2, 2.2, 1.4 Hz, 1H), 5.20 (ddd,J=10.2, 1.7, 1.3 Hz, 1H), 5.29 (dq, J=17.2, 1.7 Hz, 1H), 5.81 (ddd,J=17.2, 10.2, 6.7 Hz, 1H), 5.93 (dddd, J=17.2, 10.2, 6.0, 5.2 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=18.7, 25.8, 28.5, 28.8, 29.0, 29.1,29.3, 33.7, 64.9, 71.0, 74.0, 114.1, 117.7, 134.1, 139.1, 173.4.

(RS)-3-Methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one (x=1, y=8, R¹=Me,R²=H): 59.6 mg (0.21 mmol) of Ti(OiPr)₄ are added to a solution of 187mg (0.7 mmol) of dec-9-enyl (RS)-2-allyloxy-propionate in 220 ml ofCH₂Cl₂ and the mixture is refluxed for 1 h. 16.4 mg (0.02 mmol) ofbenzylidene-bis-(tricyclohexylphosphine)-dichlororuthenium, dissolved in5 ml of CH₂Cl₂, are then added and the mixture is refluxed for 20 h.After cooling to room temperature, the reaction solution is washed with2×50 ml of 1N HCl, then dried over Na₂SO₄ before being filtered over ashort silica gel column. The solvent is then removed on a rotaryevaporator, giving 160 mg (95%) of a colorless oil.

Odor: musk, sweet-flowery, ambergris, erogenous, reminiscent of ambrettemusk.

Isomerism details: excess:deficit isomer

¹H-NMR (400 MHz, CDCl₃): δ(ppm)=1.23-1.46 (m, 10H), 1.40:1,41 (d,J=6.9:6.9 Hz, 3H), 1.57-1.74 (m, 2H), 1.91-2.14 (m, 2H), 3.86-4.12 (m,2H), 4.01:4.03 (q, J=6.9:6.9 Hz, 1H), 4.20-4.44 (m, 2H), 5.46-5.67 (m,2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=18.7:18.9, 23.3, 24.8, 26.0, 26.3, 26.8,27.6, 31.0, 64.4:65.3, 71.3:65.7, 72.8:73.0, 127.1:126.2, 135.4:134.3,173.7.

(RS)-3-Methyl-1,4-dioxacyclopentadecan-2-one (x=1, y=8, R¹=Me, R²=H): 12mg of Pd/C are added to a solution of 240 mg (1 mmol) of(RS)-3-methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one and 10 ml ofisopropanol. Hydrogenation is then carried out at room temperature andatmospheric pressure. After 3 h, the mixture is filtered over Celitewith suction and the solvent is removed on a rotary evaporator. Flashchromatography (cyclohexane/EtOAc=30:1, R_(f)=0.28) over silica gelgives 177 mg (74%) of a colorless oil.

Odor: musk, sweet-flowery, ambergris, erogenous, animalic, reminiscentof ambrette musk and nitromusk.

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.20-1.50 (m, 14H), 1.40 (d, J=6.8 Hz,3H), 1.57-1.80 (m, 4H), 3.50 (m, 2H), 3.99 (q, J=6.8 Hz, 1H), 4.20 (ddd,J=6.1, 4.7, 1.3 Hz, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=18.6, 23.3, 24.5, 24.9, 25.2, 26.2,26.3, 26.5, 27.7, 28.2, 64.9, 70.4, 75.6, 174.1.

Example 2.2 (S)-(−)-3-Methyl-1,4-dioxacyclopentadecan-2-one

Ethyl (S)-(−)-2-allyloxy-propionate (x=1, R¹=Me, R²=H, R³=Et): 7.08 g(60 mmol) of ethyl (S)-(−)-lactate are introduced into 120 ml ofcyclohexane, and 25.0 g (120 mmol) of allyl trichloroacetimidate,dissolved in 30 ml of cyclohexane, are added thereto. 0.55 ml (6 mmol)of trifluoromethanesulfonic acid are then added and the mixture isstirred for 16 h. When the reaction is complete, the precipitatedtrichloroacetamide is filtered off with suction and washed withcyclohexane. The filtrate is washed with saturated NaHCO₃ solution,after which the organic phase is dried over Na₂SO₄, filtered andevaporated on a rotary evaporator. Flash-chromatographic purification(cyclohexane/EtOAc=10:1; R_(f)=0.27) gives 6.9 g (72%) of a colorlessliquid.

Angle of rotation: [α]_(D) ²⁰=−70.1°.

Enantiomeric purity: ee=95.2%.

Dec-9-enyl (S)-(−)-2-allyloxy-propionate (x=1, y=8, R¹=Me, R²=H): 3.0 g(19 mmol) of ethyl 2-allyloxypropionate are introduced into 4.5 g (28.5mmol) of 9-decen-1-ol, and 0.56 g (2 mmol) of Ti(OiPr)₄ are added. Themixture is then heated to 80° C. and stirred at a reduced pressure of400 mbar for 5 h. A few drops of water are then added and the crudeproduct is purified by means of flash chromatography(cyclohexane/EtOAc=25:1; R_(f)=0.21), giving 4.1 g (81%) of a colorlessoil.

Angle of rotation: [α]_(D) ²⁰=−46.60°.

Enantiomeric purity: ee=94.8%.

The ring closure olefin metathesis and subsequent hydrogenation werecarried out analogously to the procedures described under 2.1. Only theangle of rotation and the enantiomeric purity are thus given here:

(S)-(−)-3-Methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one (x=1, y=8,R¹=Me, R²=H)

Odor: weakly musk, sweet-flowery, erogenous, weaker than the enantiomermixture.

Angle of rotation: [α]_(D) ²⁰=−20.0°.

Enantiomeric purity: the enantiomeric purity for the two E/Z isomerscannot be determined due to peak overlaps.

(S)-(−)-3-Methyl-1,4-dioxacyclopentadecan-2-one (x=1, y=8, R¹=Me, R=H)

Odor: musk, sweet-flowery, ambergris, erogenous, animalic, reminiscentof ambrette musk and nitromusk, weaker than the enantiomer mixture.

Angle of rotation: [α]_(D) ²⁰=−23.0°.

Enantiomeric purity: ee=95.2%.

The following antipodes are accessible in a corresponding way. Forthese, only the angle of rotation and the enantiomeric purity aretherefore given:

Example 2.3 (R)-(+)-3-Methyl-1,4-dioxacyclopentadecan-2-one

Isobutyl R)-(+)-2-allyloxy-propionate (x=1, R¹=Me, R²=H, R³=i-Bu)

Angle of rotation: no angle of rotation determination since the compoundwas further used as crude product.

Enantiomeric purity: ee=99%.

Dec-9-enyl (R)-(+)-2-allyloxy-propionate (x=1, y=8, R¹=Me, R²=H)

Angle of rotation: No angle of rotation determination since the compoundwas further used as crude product.

Enantiomeric purity: ee=99%.

(R)-(+)-3-Methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one (x=1, y=8,R¹=Me, R²=H)

Odor: musk, sweet-flowery, ambergris, erogenous, reminiscent of ambrettemusk, more musk-like and erogenous than the (S)-(−)-enantiomer.

Angle of rotation: [α]_(D) ²⁰=+20.0°.

Enantiomeric purity: the enantiomeric purity for the two E/Z isomerscannot be determined due to peak overlapping.

(R)-(+)-3-Methyl-1,4-dioxacyclopentadecan-2-one (x=1, y=8, R¹=Me, R²=H)

Odor: musk, sweet-flowery, ambergris, erogenous, animalic, reminiscentof ambrette musk and nitromusk, stronger than the (S)-(−)-enantiomer.

Angle of rotation: [α]_(D) ²⁰=+20.4°.

Enantiomeric purity: ee=99%.

The following compounds of Examples 3.1, 3.2, 3.3 have been preparedanalogously to the procedures described under Example 2.1. For these,only the spectroscopic data are therefore given:

Example 3.1 (RS)-3-Methyl-1,4-dioxacyclohexadecan-2-one

Undec-10-enyl (RS)-2-allyloxy-propionate (x=1, y=9, R¹=Me, R²=H)

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.25-1.44 (m, 12), 1.42 (d, J=6.9 Hz,3H), 1.57-1.76 (m, 2), 1.98-2.11 (m, 2H), 3.94 (ddd, J=12.5, 6.1, 1.3Hz, 2H), 4.01 (q, J=6.9 Hz, 1H), 4.13 (m, 2H), 4.93 (ddd, J=10.2, 2.2,1.2 Hz, 1H), 4.99 (ddd, J=17.1, 2.2, 1.5 Hz, 1H), 5.20 (ddd, J=10.3,1.7, 1.1 Hz, 1H), 5.29 (dq, J=17.3, 1.7 Hz, 1H), 5.81 (ddd, J=17.1,10.2, 6.7 Hz, 1H), 5.95 (ddd, J=17.3, 10.3, 6.2 Hz, 1H).

¹³ C-NMR (50 MHz, CDCl₃): δ(ppm)=18.7, 25.8, 28.5, 28.9, 29.0, 29.1,29.3, 29.4, 33.8, 64.9, 71.0, 74.0, 114.1, 117.6, 134.1, 139.1, 173.4.

(RS)-3-Methyl-1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one (x=1, y=9, R¹=Me,R²=H)

Odor: musk, sweet-woody, ambergris, erogenous, animalic, reminiscent ofambrette musk.

Isomerism details: excess:deficit isomer

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.22-1.53 (m, 12 H), 1.40:1.42 (d,J=6.8:6.8 Hz, 3H), 1.65 (m, 2H), 2.11:2.05 (m, 2H), 3.96-4.36 (m, 4H),4.10:4.02 (q, J=6.8:6.8 Hz, 1H), 5.48-5.69 (m, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=18.2:18.8, 24.9, 25.4, 26.1, 26.3, 27.1,27.5, 28.0, 31.3, 64.6:64.7, 69.8:66.2, 71.5:74.1, 126.4:125.9,135.7:133.6, 173.4.

(RS)-3-Methyl-1,4-dioxacyclohexadecan-2-one (x=1, y=9, R¹=Me, R²=H)

Odor: musk, sweet-woody, ambergris, erogenous, animalic, reminiscent ofambrette musk and nitromusk.

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.25-1.50 (m, 16H), 1.40 (d, J=6.7 Hz,3H), 1.53-1.76 (m, 4H), 3.31-3.63 (m, 2H), 3.99 (q, J=6.7 Hz, 1H), 4.21(dd, J=5.6, 5.0 Hz, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=18.1, 24.2, 24.6, 25.4, 26.5, 26.6,26.7, 26.8, 26.9, 28.4, 28.7, 64.8, 69.9, 75.5, 173.6.

Example 3.2 (S)-(−)-3-Methyl-1,4-dioxacyclohexadecan-2-one

Undec-10-enyl (S)-(−)-2-allyloxy-propionate (x=1, y=9, R¹=Me, R²=H):

Angle of rotation: [α]_(D) ²⁰=−36.0°.

Enantiomeric purity: ee=94.6%.

(S)-(−)-3-Methyl-1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one (x=1, y=9,R¹=Me, R²=H)

Odor: weakly musk, sweet-woody, erogenous.

Angle of rotation: [α]_(D) ²⁰=−23.0°.

Enantiomeric purity: the enantiomeric purity for the two E/Z isomerscannot be determined due to peak overlapping.

(S)-(−)-3-Methyl-1,4-dioxacycloexadecan-2-one (x=1, y=9, R¹=Me, R²=H)

Odor: musk, sweet-woody, ambergris, erogenous, animalic, reminiscent ofambrette musk and nitromusk, weaker than the enantiomer mixture.

Angle of rotation: [α]_(D) ²⁰=−16.0°.

Enantiomeric purity: ee=95.2%.

Example 3.3 (R)-(+)-3-Methyl-1,4-dioxacyclohexadecan-2-one

Undec-10-enyl (R)-(+)-2-allyloxy-propionate (x=1, y=9, R¹=Me, R²=H)

Angle of rotation: no angle of rotation determination since the compoundwas used further as crude product.

Enantiomeric purity: ee=99%.

(R)-(+)-3-Methyl-1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one (x=1, y=9,R¹=Me, R²=H)

Odor: musk, sweet-woody, ambergris, erogenous, animalic, reminiscent ofambrette musk, stronger than the enantiomer mixture.

Angle of rotation: [α]_(D) ²⁰=+28.2°.

Enantiomeric purity: the enantiomeric purity for the two E/Z isomerscannot be determined due to peak overlapping.

(R)-(+)-3-Methyl-1,4-dioxacyclohexadecan-2-one (x=1, y=9, R¹=Me, R²=H)

Odor: musk, sweet-woody, ambergris, erogenous, animalic, reminiscent ofambrette musk and nitromusk, stronger than the (S)-(−)-enantiomer.

Angle of rotation: [α]_(D) ²⁰=+15.4°.

Enantiomeric purity: ee=99%.

Example 4 1,4-Dioxacyclopentadecan-2-one

2-Allyloxy-acetic acid (x=1, Y=OH, R¹, R²=H): 1.8 g (30 mmol) of allylalcohol, dissolved in 10 ml of THF, are added to a suspension of 2.4 g(60 mmol) of NaH in 30 ml of THF. 3.4 g (25 mmol) of bromoacetic acid,dissolved in 20 ml of THF, are then added dropwise. The mixture is thenrefluxed for 6 h. After this time, the mixture is cooled and thereaction is quenched with 40 ml of 2N HCl. The aqueous phase isextracted three times with EtOAc. The combined organic phases are driedover Na₂SO₄, filtered and evaporated to dryness on a rotary evaporator,giving 3.8 g of crude product (GC purity 90.3%), which is used in thenext reactions without further purification.

Dec-9-enyl 2-allyloxy-acetate (x=1, y=8, R¹, R² =H): 2.5 g of crude2-allyloxyacetic acid are introduced into 40 ml of toluene, and 4.7 g(30 mmol) of 9-decen-1-ol and 0.38 g (2.0 mmol) of p-toluenesulfonicacid are added. The mixture is then heated with a water separator untilvisible amounts of water no longer separate out. The mixture is thencooled, and the organic phase is washed once with saturated NaHCO₃solution, dried over Na₂SO₄ and filtered, and the product is freed fromthe solvent. Flash chromatography (cyclohexane/EtOAc=20:1, R_(f)=0.29)gives 3.1 g (62%) of dec-9-enyl 2-allyloxy-acetate as a colorless oil.

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.20-1.45 (m, 10H), 1.55-1.73 (m, 2H),1.96-2.02 (m, 2H), 4.08 (s, 2H), 4.10 (dt, J=5.8, 1.2 Hz, 2H), 4.16 (t,J=6.7 Hz, 2H), 4.93 (ddd, J=10.3, 2.2, 1.2 Hz, 1H), 4.99 (ddd, J=17.3,2.2, 1.5 Hz, 1H), 5.24 (ddd, J=10.3, 1.7, 1.2 Hz, 1H), 5.31 (dq, J=17.3,1.7 Hz, 1H), 5.81 (ddd, J=17.3, 10.3, 6.6 Hz, 1H), 5.93 (ddd, J=17.3,10.3, 5.8 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=25.8, 28.5, 28.8, 29.0, 29.1, 29.3,33.7, 64.9, 67.1, 72.3, 114.1, 118.2, 133.7, 139.1, 170.4.

The ring closure olefin metathesis and also the subsequent hydrogenationare carried out analogously to the synthesis procedures described underExample 2.1, meaning that only the spectroscopic data are given here:

1,4-Dioxa-(E/Z)-6-cyclopentadecen-2-one (x=1, y=8, R¹, R²=H)

Odor: musk, metallic, reminiscent of a hot iron.

Isomerism details: excess:deficit isomer

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.20-1.50 (m, 10H), 1.55-1.80 (m, 2H),2.0-2.16 (m, 2H), 4.09 (s, 2H), 4.11-4.33 (m, 4H), 5.43-5.75 (m, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=23.1, 25.2, 26.1, 26.5, 27.3, 27.5,31.2, 64.2:65.3, 65.7:66.1, 72.6, 126.6:125.5, 136.6:135.6, 171.2.

4-Dioxacyclopentadecan-2-one (x=1, y=8, R¹, R²=H)

Odor: musk, sweet-flowery, erogenous, reminiscent of musk ambrette.

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.30-1.51 (m, 14H), 1.60-1.80 (m, 4H),3.52 (t, J=6.6 Hz, 2H), 4.11 (s, 2H), 4.22 (dd, J=5.1, 4.4 Hz, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=23.7, 24.7, 25.3, 25.5, 26.2, 26.6,26.9, 27.7, 28.0, 65.3, 69.3, 71.9, 171.3.

The following compounds are accessible in a corresponding way. Forthese, only the spectroscopic data are therefore given:

Example 5 1,4-Dioxacyclohexadecan-2-one

Undec-10-enyl 2-allyloxy-acetate (x=1, y=9, R¹, R²=H)

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.20-1.45 (m, 12H), 1.55-1.73 (m, 2H),1.96-2.11 (m, 2H), 4.08 (s, 2H), 4.10 (dt, J=5.8, 1.4 Hz, 2H), 4.16 (t,J=6.7 Hz, 2H), 4.93 (ddd, J=10.2, 2.2, 1.3 Hz, 1H), 4.99 (ddd, J=17.1,2.2, 1.4 Hz, 1H), 5.24 (ddd, J=10.2, 1.5, 1.2 Hz, 1H), 5.31 (dq, J=17.2,1.5 Hz, 1H), 5.81 (ddd, J=17.2, 10.2, 6.7 Hz, 1H), 5.93 (ddd, J=17.2,10.2, 5.8 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=25.8, 28.5, 28.9, 29.0, 29.2, 29.3,29.4, 33.8, 65.0, 67.1, 72.3, 114.1, 118.1, 133.7, 139.1, 170.4.

1,4-Dioxa-(E/Z)-6-cyclohexadecen-2-one (x=1, y=9, R¹, R²=H)

Odor: musk, woody, technically reminiscent of a hot iron.

Isomerism details: excess:deficit isomer

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.20-1.50 (m, 12H), 1.61-1.78 (m, 2H),2.00-2.20 (m, 2H), 4.07-4.14 (m, 2H), 4.10:4.11 (s, 2H), 4.18-4.29 (m,2H), 5.41-5.76 (m, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=25.3, 25.9, 26.4, 26.9, 27.6, 27.7,27.9, 31.6, 64.7:66.7, 64.8:66.8, 70.8, 125.8:125.2, 137.3:135.1, 170.5.

1,4-Dioxacyclohexadecan-2-one (x=1, y=9, R¹, R²=H)

Odor: musk, ambergris, erogenous, animalic, reminiscent of musktincture, musk ambrette and nitromusk.

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.25-1.51 (m, 16H), 1.55-1.75 (m, 2H),3.53 (t, J=5.8 Hz, 2H), 4.08 (s, 2H), 4.24 (dd, J=5.2, 5.1 Hz, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=24.2, 24.3, 25.3, 25.4, 26.5, 26.6,26.8, 26.9, 28.1, 28.5, 64.8, 69.0, 71.2, 170.5.

Example 6 1,4-Dioxa-(E/Z)-7-cyclohexadecen-2-one

Dec-9-enyl 2-(3-butenyloxy)-acetate (x=2, y=8, R¹, R²=H)

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.20-1.41 (m, 10H), 1.57-1.71 (m, 2H),1.98-2.12 (m, 2H), 2.40 (qd, J=6.7, 1.4 Hz, 2H), 3.60 (t, J=6.6 Hz, 2H),4.09 (s, 2H), 4.15 (t, J=6.8 Hz, 2H), 4.92 (ddd, J=10.3, 2.2, 1.3 Hz,1H), 4.95 (ddd, J=16.4, 2.2, 1.4 Hz, 1H), 5.11 (ddd, J=10.3, 1.5, 1.2Hz, 1H), 5.18 (dq, J=16.4, 1.4 Hz, 1H), 5.75 (ddd, J=16.4, 10.3, 6.6 Hz,1H), 5.93 (ddd, J=16.4, 10.3, 5.8 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=25.8, 28.6, 28.9, 29.0, 29.2, 29.3,33.8, 34.0, 65.0, 68.3, 71.0, 114.2, 116.7, 134.8, 139.1, 170.6.

1,4-Dioxa-(E/Z)-7-cyclohexadecen-2-one (x=2, y=8, R¹, R²=H)

Odor: musk, erogenous, sweet-woody, metallic, reminiscent of a hot iron.

Isomerism details: excess:deficit isomer

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.20-1.50 (m, 10H), 1.59-1.73 (m, 2H),1.98-2.12 (m, 2H), 2.25-2.48 (m, 2H), 3.44-3.62 (m, 2H), 4.09:4.11 ( s,2H), 4.18-4.30 (m, 2H), 5.40-5.50 (m, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=23.8, 25.3, 26.7, 26.8, 27.5, 27.6,31.6, 33.1, 65.0:64.2, 69.3:69.2, 71.3:71.4, 127.5:125.0, 132.2, 170.4.

Example 7 1,4-Dioxa (E/Z)-7-cycloheptadecen-2-one

Undec-10-enyl 2-(3-butenyloxy)-acetate (x=2, y=9, R¹, R²=H)

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.20-1.48 (m, 12H), 1.55-1.74 (m, 2H),1.97-2.12 (m, 2H), 2.40 (qd, J=6.9, 1.2 Hz, 2H), 3.60 (t, J=6.7 Hz, 2H),4.0 (s, 2H), 4.15 (t, J=6.8 Hz, 2H), 4.92 (ddd, J=10.2, 2.2, 1.4 Hz,1H), 4.96 (ddd, J=16.3, 2.2, 1.4 Hz, 1H), 5.08 (ddd, J=10.3, 1.4, 1.2Hz, 1H), 5.17 (dq, J=16.5, 1.4 Hz, 1H), 5.75 (ddd, J=16.3, 10.3, 6.5 Hz,1H), 5.93 (ddd, J=16.5, 10.3, 5.7 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=25.8, 28.5, 28.8, 29.0, 29.1, 29.3,29.4, 33.8, 34.0, 64.9, 68.3, 71.0, 114.1, 116.6, 134.7, 139.1, 170.5.

1,4-Dioxa-(E/Z)-7-cycloheptadecen-2-one (x=2, y=9, R¹, R²=H)

Odor: musk, erogenous, sweet-woody.

Isomerism details: excess:deficit isomer

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.21-1.51 (m, 12H), 1.60-1.78 (m, 2H),2.00-2.18 (m, 2H), 2.26-2.50 (m, 2H), 3.48-3.64 (m, 2H), 4.12 (s, 2H),4.19-4.29 (m, 2H), 5.34-5.51 (m, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=26.9, 27.6, 28.0, 28.1, 28.2, 28.4,28.5, 31.5, 32.9, 65.4:65.2, 69.2:68.9, 71.6, 126.7:124.4, 132.6, 170.7

Example 8 (RS)-3-Methyl-1,4-dioxa-(E/Z)-7-cyclohexadecen -2-one

Dec-9-enyl 2-(3-butenyloxy)-propionate (x=2, y=8, R¹=Me, R²=H)

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.26-1.44 (m, 10H), 1.40 (d, J=6.9 Hz,3H), 1.60-1.70 (m, 2H), 1.98-2.07 (m, 2H), 2.37 (qt, J=6.9, 1.5 Hz, 2H),3.42 (dt, J=8.5, 6.8 Hz, 1H), 3.64 (dt, J=8.5, 6.8 Hz, 1H), 3.81 (q,J=6.8 Hz, 1H), 4.14 (td, J=6.8, 2.6 Hz, 2H), 4.90 (ddd, J=10.2, 2.2, 1.4Hz, 1H), 4.95 (ddd, J=16.3, 2.2, 1.4 Hz, 1H), 5.07 (ddd, J=10.3, 1.4,1.2 Hz, 1H), 5.15 (dq, J=16.5, 1.4 Hz, 1H), 5.74 (ddd, J=16.3, 10.3, 6.5Hz, 1H), 5.91 (ddd, J=16.5, 10.3, 5.7 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=18.7, 25.8, 28.5, 28.8, 28.9, 29.1,29.3, 33.7, 34.1, 64.8, 69.4, 74.9, 114.0, 116.4, 134.7, 139.0, 173.3.

(RS)-3-Methyl-1,4-dioxa-(E/Z)-7-cyclohexadecen-2-one (x=2, y=8, R¹=Me,R²=H)

Odor: musk, woody, metallic, reminiscent of a hot iron.

Isomerism details: excess:deficit isomer

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.22-1.42 (m, 10H), 1.40:1.42 (d, J=6.8Hz, 3H), 1.55-1.72 (m, 2H), 1.96-2.09 (m, 2H), 2.19-2.38 (m,2H),3.37-3.57 (m, 2H), 3.98:4.00 (q, J=6.8 Hz, 1H), 4.10-4.30 (m, 2H),5.39-5.49 (m, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=18.2, 24.5, 24.9, 26.8, 27.1, 28.0,28.1, 31.1, 33.1, 65.0:64.1, 70.4.70.1, 76.8, 127.5:124.5, 132.1, 173.4.

Example 9 (RS)-3-Methyl-1,4-dioxacycloheptadecan-2-one

Undec-10-enyl 2-(3-butenyloxy)-propionate (x=2, y=9, R¹=Me, R²=H)

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.24-1.42 (m, 12H), 1.40 (d, J=6.8 Hz,3H), 1.58-1.70 (m, 2H), 1.97-2.10 (m, 2H), 2.37 (qt, J=6.9, 1.4 Hz, 2H),3.42 (dt, J=9.0, 6.9 Hz, 1H), 3.64 (dt, J=9.0, 6.9 Hz, 1H), 3.96 (q,J=6.8 Hz, 1H), 4.15 (td, J=6.5, 2.6 Hz, 2H), 4.91 (ddd, J=10.1, 2.2, 1.4Hz, 1H), 4.95 (ddd, J=17.0, 2.2, 1.4 Hz, 1H), 5.07 (ddd, J=10.2, 1.4,1.2 Hz, 1H), 5.15 (dq, J=17.2, 1.4 Hz, 1H), 5.74 (ddd, J=17.0, 10.1, 6.5Hz, 1H), 5.91 (ddd, J=17.2, 10.2, 5.7 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=18.6, 25.8, 28.5, 28.8, 29.0, 29.1,29.3, 29.4, 33.7, 34.1, 64.8, 69.4, 74.9, 114.0, 116.4, 134.7, 139.0,173.3.

(RS)-3-Methyl-1,4-dioxa-(E/Z)-7-cycloheptadecen-2-one (x=2, y=9, R¹=Me,R²=H)

Odor: musk, erogenous, sweet-woody.

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.20-1.44 (m, 12H), 1.40:1.42 (d, J=6.8Hz, 3H), 1.60-1.75 (m, 2H), 1.98-2.10 (m, 2H), 2.25-2.37 (m,2H),3.34-3.60 (m, 2H), 4.00:3.98 (q, J=6.8 Hz, 1H), 4.15-4.28 (m, 2H),5.40-5.50 (m, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=18.5:18.8, 25.8, 27.1, 27.5, 27.7, 27.8,28.6, 28.7, 31.6, 32.9, 65.0, 70.5:70.2, 75.5:75.7, 126.0:124.0,132.9:132.5, 173.6

(RS)-3-Methyl-1,4-dioxacycloheptadecan-2-one (x=2, y=9, R¹=Me, R²=H)

Odor: musk, sweet-woody, ambergris, erogenous, animalic, reminiscent ofambrette musk.

¹H-NMR (200 MHz, CDCl₃): δ(ppm)=1.26-1.44 (m, 18H), 1.40 (d, J=6.8 Hz,3H), 1.55-1.75 (m, 4H), 3.38-3.60 (m, 2H), 3.79 (q, J=6.8 Hz, 1H),4.10-4.30 (m, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ(ppm)=18.6, 24.7, 25.3, 26.1, 26.4, 26.6,26.7, 27.1, 27.3, 27.4, 28.6, 28.7, 64.9, 70.3, 75.5, 173.7.

Example 10

The present perfume oil is used for the perfuming of many differenttypes of cosmetic products.

Composition

Ingredients Parts by weight 1. Citrophoral Base (H&R) 5.0 2. AldehydeC10 10% in BA 5.0 3. Aldehyde C11 MOA 10% in BA 3.0 4. Farenal (H&R) 3.05. Aldehyde C11 10% in IPM 5.0 6. Citroxal 50% in DEP 2.0 7. transHex-2-enol 10% in BA 2.0 8. Vertocitral (H&R) 1.0 9. Linalyl acetate45.0 10. Citrylal (H&R) 5.0 11. Mandarinal (Firmenich) 4.0 12. Lilial(Givaudan Roure) 75.0 13. Lyral (IFF) 75.0 14. Profarnesol (H&R) 5.0 15.Nerolidol 5.0 16. Linalool 45.0 17. Geranium oil, African 5.0 18.Phenylethyl alcohol 75.0 19. Geraniol 15.0 20. Nerol 10.0 21.Hexylcinnamaldehyde alpha 50.0 22. Methyl dihydrojasmonate 15.0 23.Benzyl salicylate 100.0 24. trans,cis-2-Nonadienol 0.1% in IPM 5.0 25.Allyl ionone (Givaudan Roure) 3.0 26. Isomethyl ionone, gamma 75.0 27.Eugenol 7.0 28. Cedryl acetate 40.0 29. Sandolen (H&R) 5.0 30. Citral5.0 BA = benzyl alcohol; IPM = isopropyl myristate; DEP = diethylphtalate

The addition of

a) 355 parts by weight of 3-methyl-1,4-dioxacyclopentadecan-2-one (total1000 parts by weight) leads to a significantly perceptible harmonizationof the fresh top note with the rosy-flowery middle note. Moreover, with3-methyl-1,4-dioxacyclopentadecan-2-one, effects reminiscent ofnitromusk are achieved and the fine erogenous musk note impartsexcellent radiance and increased adhesion to the present composition. Inthis connection, the grand character of3-methyl-1,4-dioxacyclopentadecan-2-one in particular predominatescompared with compositions containing conventional musk fragrances.

b) 55 parts by weight of 3-methyl-1,4-dioxacyclopentadecan-2-one (sum700 parts by weight) impart to the composition an animalic musk notewhich is not achieved with existing musk fragrances. In addition, theoverall composition acquires body and appears grander.

What is claimed is:
 1. A macrocyclic compound of the formula

wherein the dashed bond is a single or a E/Z double bond and when thedashed bond is a double bond, the compounds are in the E or Z form,wherein compounds having a chiral center are in (R) or (S) form, or arepresent as an enantiomer mixture, wherein R¹ and R² are the same ordifferent and are a hydrogen or a lower alkyl, wherein x is a saturatedalkylene chain having 1 to 4 carbon atoms, wherein y is a saturatedalkylene chain having 4 to 10 carbon atoms, and wherein saturatedcompounds in which R¹ and R² are hydrogen and x+y=11 carbon atoms and inwhich R¹ is methyl and R² is hydrogen and x+y=8 carbon atoms areexcluded.
 2. A macrocyclic compound according to claim 1, wherein R¹ andR² are the same or different and are selected from the group consistingof hydrogen, methyl or ethyl, wherein x a is an alkylene chain having 1,2 and 4 carbon atoms, wherein y is an alkylene chain having 4, 8 and 9carbon atoms, and wherein saturated compounds in which R¹ and R² arehydrogen and x+y=11 carbon atoms and in which R¹ is methyl and R² ishydrogen and x+y=8 carbon atoms are excluded.
 3. A macrocyclic compoundaccording to claim 1, wherein the compound is selected from the groupconsisting of 1,4-dioxa(E/Z)-9-cyclotetradecen-2-one,1,4-dioxacyclotetradecan-2-one,3-methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one,3-methyl-1,4-dioxacyclopentadecan-2-one,1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one, 1,4-dioxacyclopentadecan-2-one,3-methyl-1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one,3-methyl-1,4-dioxacyclohexadecan-2-one,1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one, 1,4-dioxacyclohexadecan-2-one,1,4-dioxa-(E/Z)-7-cyclohexadecen-2-one, 1,4-dioxa(E/Z)-7-cycloheptadecen-2-one,3-methyl-1,4-dioxa-(E/Z)-7-cyclohexadecen-2-one,3-methyl-1,4-dioxa-(E/Z)-7-cycloheptadecen-2-one, and3-methyl-1,4-dioxacycloheptadecan-2-one.
 4. A doubly terminallyunsaturated 2-alkenyloxycarboxylic alkenyl ester of the formula

wherein compounds having a chiral center are in (R) or (S) form, or arepresent as an enantiomer mixture, and wherein R¹ and R² are the same ordifferent and are a hydrogen or a lower alkyl, wherein x is a saturatedalkylene chain having 1 to 4 carbon atoms, and wherein y is a saturatedalkylene chain having 4 to 10 carbon atoms.
 5. A doubly terminallyunsaturated 2-alkenyloxycarboxylic alkenyl ester according to claim 4,wherein R¹ and R² are the same or different and are selected from thegroup consisting of hydrogen, methyl and ethyl, wherein x is an alkylenechain having 1, 2 and 4 carbon atoms, and wherein y is an alkylene chainhaving 4, 8 and 9 carbon atoms.
 6. A process for the preparation ofmacrocyclic compounds of the formula

wherein the dashed bond is a single or a E/Z double bond and when thedashed bond is a double bond, the compounds are in the E or Z form,wherein compounds having a chiral center are present as an enantiomermixture, wherein R¹ and R² are the same or different and are a hydrogenor a lower alkyl, wherein x is a saturated alkylene chain having 1 to 4carbon atoms, and wherein y is a saturated alkylene chain having 4 to 10carbon atoms, comprising the steps of etherfying a starting material toform a 2-alkenyloxycarboxylic acid or a 2-alkenyloxycarboxylic ester,wherein the starting material is an alkylcarboxylic acid or esterderived in the 2 position and of the formula

wherein R¹ has the meaning given above, and R³ is selected from thegroup consisting of OH, Cl, and Br, and R⁴ is selected from the groupconsisting of OH, OMe and OEt, esterfying the 2-alkenyloxycarboxylicacid or a 2-alkenyloxycarboxylic alkenyl ester to form an unsaturated2-alkenyloxycarboxylic alkenyl ester, and then closing the open ring ofthe unsaturated 2-alkenyloxycarboxylic alkenyl ester by olefinmetathesis to form a unsaturated 1,4 dioxacycloalken 2 ones.
 7. Aprocess for the preparation of chiral macrocyclic compounds of theformula

wherein the dashed bond is a single or E/Z double bond and when thedashed bond is a double bond, the compounds are in the E and Z form,wherein compounds having a chiral center are present in(R) or (S) form,wherein R¹ is a lower alkyl, wherein x is a saturated alkylene chainhaving 1 to 4 carbon atoms, and wherein y is a saturated alkylene chainhaving 4 to 10 carbon atoms, comprising the steps of etherfying astarting material under acidic, nonracemizing conditions to form achiral (R)- or (S)-2-alkenyloxycarboxylic alkyl ester wherein thestarting material is a (S)-2- or (R)-2-hydroxycarboxylic alkyl ester ofthe formula

wherein R^(1′) has the meaning given above, and R⁵ is a C₁ to C₈ alkylradical, transesterfying the chiral (R)- or (S)-2-alkenyloxycarboxylicalkyl ester in the presence of a Lewis Acid to form an unsaturated2-alkenyloxycarboxylic alkenyl ester, and then closing the open ring ofthe unsaturated 2-alkenyloxycarboxylic alkenyl ester by olefinmetathesis to form a unsaturated 3-alkyl-1,4-dioxacycloalken-2-ones. 8.A fragrance comprising macrocyclic compounds of the formula

wherein the dashed bond is a single or a E/Z double bond and when adouble bond is present, the compounds can be in the E or Z form, whereincompounds having a chiral center are in (R) or (S) form, or are presentas an enantiomer mixture, wherein R¹ and R² are the same or differentand are a hydrogen or a lower alkyl, wherein x is a saturated alkylenechain having 1 to 4 carbon atoms, wherein y is a saturated alkylenechain having 4 to 10 carbon atoms, and wherein saturated compounds inwhich R¹ and R² are hydrogen and x+y=11 carbon atoms and in which R¹ ismethyl and R² is hydrogen and x+y=8 carbon atoms, are excluded.
 9. Afragrance composition comprising macrocyclic compounds of the formula

wherein the dashed bond is a single or a E/Z double bond and when thedashed bond is a double bond, the compounds can be in the E or Z form,wherein compounds having a chiral center are in (R) or (S) form, or arepresent as an enantiomer mixture, wherein R¹ and R² are identical ordifferent and are hydrogen or lower alkyl, wherein x is a saturatedalkylene chain having 1 to 4 carbon atoms, wherein y is a saturatedalkylene chain having 4 to 10 carbon atoms, and wherein saturatedcompounds in which R¹ and R² are hydrogen and x+y=11 carbon atoms and inwhich R¹ is methyl and R² is hydrogen and x+y=8 carbon atoms, areexcluded.
 10. The fragrance composition according to claim 9, comprising1 to 40% by weight of a macrocyclic 1,4-dioxacycloalkan-2-ones and amacrocyclic 1,4-dioxacycloalken-2-ones.
 11. The fragrance compositionaccording to claim 9, wherein the fragrance composition has a musk odor.12. The process according to claim 6, further comprising the step ofhydrogenating the unsaturated 1,4-dioxacycloalken-2-ones.
 13. Theprocess according to claim 7, further comprising the step ofhydrogenating the unsaturated 3-alkyl-1,4-dioxacycloalken-2-ones.
 14. Amacrocyclic compound according to claim 1, wherein the compound is a1,4-dioxacycloalkan-2-one or 1,4-dioxacycloalken-2-one.
 15. A processaccording to claim 6 wherein the macrocyclic compound is a1,4-dioxacycloalken-2-ones.
 16. A process according to claim 12, whereinthe macrocyclic compound is a 1,4-dioxacycloalkan-2-ones.
 17. A processaccording to claim 7, wherein the macrocyclic compound is a3-alkyl-1,4-dioxacycloalken-2-ones.
 18. A process according to claim 13,wherein the macrocyclic compound is a3-alkyl-1,4-dioxacycloalkan-2-ones.